CN111492017B

CN111492017B - Three-dimensional printing ink comprising phthalonitrile oligomers

Info

Publication number: CN111492017B
Application number: CN201980006397.6A
Authority: CN
Inventors: 金荣旲; 辛富建; 金相佑; 李承姬; 高恩皓
Original assignee: LG Chem Ltd
Current assignee: LG Chem Ltd
Priority date: 2018-09-21
Filing date: 2019-09-20
Publication date: 2022-06-07
Anticipated expiration: 2039-09-20
Also published as: EP3705541A1; US11674045B2; EP3705541A4; WO2020060266A1; US11591487B2; US20210206908A1; JP7031939B2; CN111492017A; US20210047528A1; EP3705541B1; CN111479885A; CN111479885B; WO2020060262A1; JP2021505438A

Abstract

The present invention relates to three-dimensional printing inks. According to the present invention, a three-dimensional printing ink capable of achieving viscosity and improved performance suitable for three-dimensional printing is provided.

Description

Three-dimensional printing ink comprising phthalonitrile oligomers

Technical Field

Cross Reference to Related Applications

This application claims the benefit of korean patent application No. 10-2018-0114412 and korean patent application No. 10-2018-0114413, which were filed by the korean intellectual property office at 21.9.2018, the disclosures of which are incorporated herein by reference in their entireties.

The present invention relates to three-dimensional printing inks.

Background

Three-dimensional printing (hereinafter referred to as "3D printing") is a method of preparing a three-dimensional object by arranging a binder material layer by layer on a powder bed including an inkjet printer head.

3D printing is advantageous for multi-product, small volume production compared to conventional mass production methods (e.g., injection molding), and can freely manufacture a variety of complex shapes or forms.

Depending on the kind of raw materials used, 3D printing techniques can be divided into liquid-based methods, such as stereolithography; powder-based methods such as selective laser sintering, direct metal laser sintering; solid-based methods such as layered solid fabrication, fused deposition modeling.

As a material for 3D printing, a thermosetting resin is mainly used. For example, U.S. registered patent No. 9,708,440 (2017.07.18) discloses a high-temperature 3D printing ink capable of 3D printing through two stages of curing.

However, in general, high-temperature 3D printing ink for 3D printing takes a long time to cure, and it may not have a viscosity suitable for 3D printing. Therefore, there are limitations as follows: additional components for accelerating curing should be used during 3D printing using the high temperature 3D printing ink.

Disclosure of Invention

Technical problem

An object of the present invention is to provide a three-dimensional printing ink capable of achieving viscosity and improved performance suitable for three-dimensional printing.

Technical scheme

According to the present invention, there is provided a three-dimensional printing ink comprising (a) a phthalonitrile oligomer containing one or more repeating units represented by the following chemical formula 1 and (b) a curing agent.

[ chemical formula 1]

In the chemical formula 1, the first and second,

R^aand R^bEach independently is hydrogen, C_1-5Alkyl radical, C_1-3Hydroxyalkyl radicals, or from

The group of the formula (I) is,

l is a direct bond or unsubstituted or C_1-5Alkyl substituted C_1-5An alkylene group or a substituted alkylene group,

Z^aand Z^bEach independently of the others is hydrogen or

And Z contained in the repeating unit represented by chemical formula 1^aAnd Z^bAt least one of which is

The group of (a) or (b),

p is a number from 1 to 10,

q is 0 or 1, and

n is the polymerization degree of the repeating unit represented by chemical formula 1.

Hereinafter, a three-dimensional printing ink according to an embodiment of the present invention will be described in detail.

First, technical terms used herein are merely to illustrate specific embodiments and are not intended to limit the present invention.

The singular forms "a", "an" and "the" include plural referents unless the content clearly dictates otherwise.

As used herein, the term "comprising" is intended to mean that the practiced feature, quantity, step, constituent, or combination thereof is present, and is not intended to preclude the possibility of one or more other features, quantities, steps, constituents, or combination thereof being present or added.

As used herein, the symbols in the formulae

Meaning the position at which the corresponding group is attached to another group.

According to one embodiment of the present invention, there is provided a three-dimensional printing ink comprising (a) a phthalonitrile oligomer containing one or more repeating units represented by the following chemical formula 1 and (b) a curing agent.

[ chemical formula 1]

In the chemical formula 1, the first and second,

R^aand R^bEach independently of the other is hydrogen, C_1-5Alkyl radical, C_1-3Hydroxyalkyl, or from

The group of the formula (I) is,

Z^aand Z^bEach independently of the other is hydrogen or

The group of (a) or (b),

p is a number from 1 to 10,

q is 0 or 1, and

As a result of continuous research, the present inventors determined that phthalonitrile oligomers comprising one or more repeating units represented by chemical formula 1 have a low softening point and thus can achieve excellent processability.

The phthalonitrile oligomer has a large molecular weight compared to the conventional phthalonitrile monomer, and thus can maintain the melt viscosity above a certain level even under melting conditions. In particular, the phthalonitrile oligomer can have a melt viscosity that can be controlled within a wide range by controlling the molecular weight.

The 3D printing ink containing the phthalonitrile oligomer can have both excellent wettability for the filler and a suitable melt viscosity. Therefore, the 3D printing ink can be used not only by itself but also exhibits excellent workability in 3D printing using another component such as metal.

Hereinafter, components that can be contained in the 3D printing ink will be explained.

(a) Phthalonitrile oligomers

According to an embodiment of the present invention, in the 3D printing ink, a phthalonitrile oligomer containing one or more repeating units represented by the following chemical formula 1 is included.

[ chemical formula 1]

In the chemical formula 1, the reaction mixture is,

R^aand R^bEach independently is hydrogen, C_1-5Alkyl radical, C_1-3Hydroxyalkyl, or from

The group of the formula (I) is,

Z^aand Z^bEach independently of the others is hydrogen or

The group of (a) or (b),

p is a number from 1 to 10,

q is 0 or 1, and

As used herein, the term "substituted or unsubstituted" includes mono-or poly-substituted or unsubstituted with one or more substituents.

As used herein, "alkyl" may be straight or branched. Preferably, the carbon number of the alkyl group is 1 to 5 or 1 to 3. Specifically, the alkyl group may be a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methyl-butyl group, a 1-ethyl-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, etc.

As used herein, "hydroxyalkyl" means a group in which the alkylene group is terminally substituted with a hydroxyl group. For example, the hydroxyalkyl group may be hydroxymethyl (-CH)₂OH), hydroxyethyl (-CH)₂CH₂OH), hydroxypropyl (-CH)₂CH₂CH₂OH), and the like.

As used herein, "aryl" may be a monocyclic aryl or a polycyclic aryl. Preferably, the carbon number of the aryl group is 6 to 30. Specifically, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a naphthyl group, an anthryl group, a phenanthryl group,

A base,

And fluorenyl and the like.

As used herein, "direct bond" means that there is no atom at the corresponding position, and the groups on both sides are directly connected to each other.

(a) The phthalonitrile oligomer includes one or more repeating units represented by chemical formula 1.

Preferably, the (a) phthalonitrile oligomer may include one or two or three repeating units represented by chemical formula 1.

In the case where (a) the phthalonitrile oligomer includes two or more repeating units represented by chemical formula 1, the structures of the respective repeating units may be different from each other.

In chemical formula 1, R^aAnd R^bEach independently is hydrogen, C_1-5Alkyl radical, C_1-3Hydroxyalkyl, or from

Wherein L is a direct bond or unsubstituted or C_1-5Alkyl substituted C_1-5An alkylene group.

In chemical formula 1, Z^aAnd Z^bEach independently of the others is hydrogen or

Provided that Z contained in the repeating unit represented by chemical formula 1 is Z^aAnd Z^bAt least one of which is

A group of (1).

In chemical formula 1, p is 1 to 10, or 1 to 5, or 1 to 2.

In chemical formula 1, q is 0 or 1.

In chemical formula 1, n is the degree of polymerization of the repeating unit.

According to an embodiment of the present invention, the phthalonitrile oligomer may be represented by one of the following chemical formulae a to D.

[ chemical formula A ]

[ chemical formula B ]

[ chemical formula C ]

[ chemical formula D ]

In the chemical formulae a to D,

R¹to R⁴Each independently is hydrogen, C_1-5Alkyl radical, C_1-3Hydroxyalkyl, or from

A group represented by, and L101 is a direct bond or unsubstituted or C_1-5Alkyl substituted C_1-5An alkylene group or a substituted alkylene group,

Z¹to Z⁵Each independently of the others is hydrogen or

And Z in each formula¹To Z⁵At least one of which is

A group of (1).

p1 is 1 to 10, and

n1 and m are the respective degrees of polymerization of the respective repeating units.

According to an embodiment of the present invention, formula a may be represented by the following formulae a-1 to a-3.

[ chemical formula A-1]

[ chemical formula A-2]

[ chemical formula A-3]

In the chemical formulae A-1 to A-3,

Z¹¹to Z⁶¹Each independently of the others is hydrogen or

And Z contained in each chemical formula¹¹To Z⁶¹At least one of which is

The group of (a) or (b),

L¹to L³Each independently is warp C_1-5Alkyl substituted C_1-5Alkylene, and

n2 is the degree of polymerization of each repeating unit.

Specifically, the chemical formula A-3 may be represented by the following chemical formula (A-3)'.

[ chemical formula (A-3)' ]

In the formula (A-3)', Z¹To Z⁶As defined in formula a-3.

According to an embodiment of the present invention, formula B may be represented by the following formula B-1.

[ chemical formula B-1]

In the formula B-1, Z¹²To Z⁵²、R¹L101 and n3 are each independently related to Z in formula B¹To Z⁵、R¹L101 and n are the same.

According to an embodiment of the present invention, the chemical formula C may be represented by the following chemical formula C-1.

[ chemical formula C-1]

In the formula C-1, Z¹³To Z⁵³N3 and m3 are respectively related to Z in the chemical formula C¹To Z⁵N and m are the same.

According to an embodiment of the present invention, formula D may be represented by the following formula D-1.

[ chemical formula D-1]

In the formula D-1, Z¹⁴To Z⁵⁴P2 and n4 are respectively related to Z in chemical formula D¹To Z³P and n are the same.

Meanwhile, (a) the phthalonitrile oligomer may be prepared by reacting an oligomer comprising one or more repeating units represented by the following chemical formula 1 '(hereinafter, referred to as "oligomer of chemical formula 1') with a phthalonitrile compound (e.g., 4-nitrophthalonitrile).

[ chemical formula 1' ]

In the chemical formula 1', the reaction mixture is,

R^a′and R^b′Each independently is hydrogen, C_1-5Alkyl radical, C_1-3Hydroxyalkyl, or from

The group of the formula (I) is,

l is a direct bond or unsubstituted or C_1-5Alkyl substituted C_1-5An alkylene group, which is a cyclic alkylene group,

p is a number from 1 to 10,

q is 0 or 1, and

n is the degree of polymerization of the repeating unit represented by chemical formula 1'.

The phthalonitrile group is bonded to the-OH group contained in the oligomer of chemical formula 1 'by the reaction of the oligomer of chemical formula 1' with a phthalonitrile compound, thereby synthesizing (a) a phthalonitrile oligomer.

In the above reaction, introduced into the repeating unit of chemical formula 1

Radical (corresponding to Z)^aAnd Z^bGroup (b) may vary depending on the reaction rate of the oligomer of chemical formula 1' with the phthalonitrile compound.

As the oligomer of chemical formula 1', those prepared by a general method in the art to which the present invention pertains may be used.

In addition, as the oligomer of chemical formula 1 ', a commercial product including one or more repeating units represented by chemical formula 1' may be used.

Meanwhile, the weight average molecular weight of the (a) phthalonitrile oligomer may be 1,000g/mol to 30,000 g/mol.

Throughout the present specification, the term "weight average molecular weight" is a numerical value in terms of polystyrene as a standard measured by GPC (gel permeation chromatography). In the present specification, the term "molecular weight" means a weight average molecular weight unless otherwise described.

As a non-limiting example, molecular weight was measured using Agilent PL-GPC 220 equipped with a PolarGel MIXED-L column (Polymer Laboratories) of 300mm length. The measurement temperature was 65 ℃, dimethylformamide was used as a solvent, and the flow rate was 1 mL/min. Samples were prepared at a concentration of 10mg/10mL and then fed in an amount of 100. mu.L. The Mw and Mn values were obtained with reference to a calibration curve formed using polystyrene standards. As polystyrene standards, 8 kinds having a molecular weight (g/mol) of 580/3,940/8,450/31,400/70,950/316,500/956,000/4,230,000 were used.

(a) The phthalonitrile oligomer can be given a molecular weight in a wide range from 1,000 to 30,000 g/mol. By controlling the molecular weight, rheological properties of the (a) phthalonitrile oligomer, such as softening point, melt viscosity, etc., can be controlled.

Meanwhile, the 3D printing ink may contain a phthalonitrile compound known in the art in addition to the (a) phthalonitrile oligomer.

As a non-limiting example, as the phthalonitrile compound, there can be mentioned compounds described in U.S. patent No. 4,408,035, U.S. patent No. 5,003,039, U.S. patent No. 5,003,078, U.S. patent No. 5,004,801, U.S. patent No. 5,132,396, U.S. patent No. 5,139,054, U.S. patent No. 5,208,318, U.S. patent No. 5,237,045, U.S. patent No. 5,292,854, U.S. patent No. 5,350,828, and the like.

Preferably, the 3D printing ink may further include (a') a phthalonitrile compound represented by the following chemical formula P1.

[ chemical formula P1]

In the formula P1, R^P11To R^P16Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, a group of the formula P2 below, or a group of the formula P3 below, and R^P11To R^P16Two or more of which are a group of the following formula P2 or a group of the following formula P3,

[ chemical formula P2]

In the chemical formula P2, the chemical formula P,

L^P2is a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -S (═ O) -, or-S (═ O)₂-，

R^P21To R^P25Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, or cyano, and R^P21To R^P25Two or more of which are cyano groups.

[ chemical formula P3]

In the chemical formula P3, the chemical formula P,

L^P3is a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -S (═ O) -, or-S (═ O)₂-，

R^P31To R^P35Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, or a group of the formula P2, and R^P31To R^P35One or more of which are groups of formula P2.

As a non-limiting example, the (a ') phthalonitrile compound may be a compound represented by the following chemical formula P1'.

[ chemical formula P1' ]

In the chemical formula P1', the chemical formula P,

L^P2and L^P3Each independently a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -S (═ O) -, or-S (═ O)₂-。

R^P11To R^P16、R^P21To R^P25And R^P31To R^P35Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy, or C_6-30And (4) an aryl group.

In the case where the 3D printing ink contains (a) a phthalonitrile oligomer and (a') a phthalonitrile compound represented by formula P1, it is preferable that the (a) phthalonitrile oligomer is contained in a content of 20% by weight or more based on the total weight of the phthalonitrile component.

That is, in order to sufficiently obtain the effect resulting from the application of the (a) phthalonitrile oligomer, it is preferable that the (a) phthalonitrile oligomer is contained in a content of 20 wt% or more or 20 wt% to 100 wt% in the phthalonitrile component applied to the 3D printing ink.

(a) The content of the phthalonitrile oligomer may be controlled in the phthalonitrile component in the range of from 20 to 100% by weight, as desired (for example, in accordance with the desired melt viscosity range).

(b) Curing agent

According to an embodiment of the present invention, the 3D printing ink comprises a curing agent.

The curing agent is a compound capable of reacting with (a) the phthalonitrile oligomer to form a phthalonitrile resin.

For example, the curing agent may be a compound containing a functional group capable of reacting with the cyano group of the (a) phthalonitrile oligomer.

Preferably, the curing agent may be a compound having one or more functional groups selected from the group consisting of amine groups, hydroxyl groups, and imide groups.

Specifically, the curing agent may be a compound represented by the following chemical formula 2.

[ chemical formula 2]

In chemical formula 2, R²¹To R²⁶Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, amine, or a group of the following chemical formula 3, and R²¹To R²⁶Two or more of which are amine groups or groups of the following chemical formula 3,

[ chemical formula 3]

In the chemical formula 3, the reaction mixture is,

L³⁰is a direct bond, C_1-5Alkylene, -O-or-S-,

R³¹to R³⁵Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, or amino, and R³¹To R³⁵At least one of which is an amine group.

As a non-limiting example, the curing agent may be a compound represented by the following chemical formula 2'.

[ chemical formula 2' ]

In the chemical formula 2', the reaction mixture is,

R²¹、R²³、R²⁴and R²⁵Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy, or C_6-30An aryl group, a heteroaryl group,

L³⁰each independently is a direct bond, C_1-5Alkylene, -O-or-S-, and

In addition, the curing agent may be a compound represented by the following chemical formula 4.

[ chemical formula 4]

In the chemical formula 4, the first and second organic solvents,

m is a tetravalent group derived from a compound represented by any one of the following chemical formulas 5 to 7,

X⁴¹and X⁴²Each independently is a divalent group derived from a compound represented by any one of the following

chemical formulae

8 and 9, and

n5 is equal to or greater than 1;

[ chemical formula 5]

In chemical formula 5, R⁵⁰To R⁵⁵Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy, or C_6-30An aryl group;

[ chemical formula 6]

In chemical formula 6, R⁶⁰To R⁶⁷Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy, or C_6-30And (4) an aryl group.

[ chemical formula 7]

In the chemical formula 7, the first and second,

R⁷⁰to R⁷⁹Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy, or C_6-30An aryl group, a heteroaryl group,

x is a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -S (═ O)₂-、-C(＝O)-O-L¹⁷-O-C(＝O)-、-L²⁷-C(＝O)-O-L³⁷-、-L⁴-O-C(＝O)-L⁵-, or-L⁶-Ar¹-L⁷-Ar²-L⁸-, wherein L¹To L⁸Each independently is a direct bond, -O-, or C_1-5Alkylene, and Ar¹And Ar²Each independently is C_6-30An arylene group.

[ chemical formula 8]

In chemical formula 8, R⁸⁰To R⁸⁵Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, hydroxy, or carboxy;

[ chemical formula 9]

In the chemical formula 9, the first and second,

R⁹⁰to R⁹⁹Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30An aryl group, a hydroxyl group, or a carboxyl group,

x' is a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -NR^a1-、-S(＝O)-、-S(＝O)₂-、-L⁹-Ar³-L¹⁰-, or-L¹¹-Ar⁴-L¹²-Ar⁵-L¹³-, wherein R^a1Is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy, or C_6-30Aryl radical, L⁹To L¹³Each independently is a direct bond, -O-, or C_1-5Alkylene, and Ar³To Ar⁵Each independently is C_6-30An arylene group.

As a non-limiting example, the curing agent may be a compound represented by the following chemical formula 4' or chemical formula 4 ″.

[ chemical formula 4' ]

[ chemical formula 4 "]

In the chemical formulae 4' and 4 ″,

x and X' are each independently a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -S (═ O)₂-、-C(＝O)-O-L¹-O-C(＝O)-、-L²-C(＝O)-O-L³-、-L⁴-O-C(＝O)-L⁵-, or-L⁶-Ar¹-L⁷-Ar²-L⁸-, wherein L¹To L⁸Each independently a direct bond, -O-, or C_1-5Alkylene radical, Ar¹And Ar²Each independently is C_6-30Arylene radicals, and

R⁹⁰to R⁹⁹Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, hydroxyl, or carboxyl.

Meanwhile, the content of the curing agent may be controlled within a range that can ensure curability given to the 3D printing ink.

As a non-limiting example, the curing agent may be included in a molar ratio of 0.01 to 1.5 moles per mole of the phthalonitrile oligomer.

As a non-limiting example, the curing agent may be included in a molar ratio of 0.01 to 1.5 moles per one mole of the phthalonitrile component included in the 3D printing ink. Among them, the "phthalonitrile component" includes (a) phthalonitrile oligomer and (a') phthalonitrile compound contained in the 3D printing ink.

If the molar ratio of the curing agent is increased, the processing window may be narrowed and thus, the workability may be decreased or high-temperature curing conditions may be required. Further, if the molar ratio of the curing agent is decreased, curability may become insufficient.

According to an embodiment of the present invention, the 3D printing ink may exhibit a melt viscosity of 1000pa.s to 100000pa.s by time sweep test using a rotational rheometer at a temperature of 200 ℃ to 280 ℃ and a frequency of 1Hz to 10 Hz.

Meanwhile, according to an embodiment of the present invention, a 3D printing ink may be provided in the state of a prepolymer which is a reaction product of (a) a phthalonitrile oligomer and (b) a curing agent.

The prepolymer means a state in which the reaction of the phthalonitrile oligomer with the curing agent in the 3D printing ink occurs to some extent (for example, a state in which polymerization of a stage or B stage occurs), but a completely cured state is not reached and appropriate fluidity is exhibited for processing.

(c) Additive agent

According to an embodiment of the present invention, the 3D printing ink may further comprise an additive.

The kind of the additive is not particularly limited.

Further, the content of the additive may be controlled within a range that does not interfere with the characteristics of the 3D printing ink.

As non-limiting examples, as additives, metal fibers, carbon fibers, glass fibers, aramid fibers, potassium titanate fibers, celluloid fibers, sepiolite fibers, ceramic fibers, acrylic fibers, barium sulfate, calcium carbonate, zirconium oxide, aluminum oxide, zirconium silicate, silica, silicon carbide, graphite, carbon nanotubes, titanium dioxide, polytetrafluoroethylene, tungsten disulfide, molybdenum disulfide, milled carbon fibers, and the like may be used.

Advantageous effects

According to the present invention, a three-dimensional printing ink capable of achieving viscosity and improved performance suitable for three-dimensional printing is provided.

Drawings

FIGS. 1 to 8 show 1H-NMR spectra of respective compounds prepared in preparation examples 1 to 8, respectively.

Detailed Description

Hereinafter, preferred embodiments are given to better understand the present invention. However, these examples are given only as illustrations of the present invention, and the present invention is not limited by these examples.

¹H-NMR (nuclear magnetic resonance) analysis

For the compounds prepared below, NMR analysis was performed according to the manufacturer's manual using a 500MHz NMR spectrometer of Agilent inc. Samples for NMR analysis were prepared by dissolving the compounds in DMSO (dimethyl sulfoxide) -d 6.

Measurement of weight average molecular weight

The weight average molecular weight (Mw) of the phthalonitrile oligomer obtained in the following preparation was measured using an Agilent PL-GPC 220 equipped with a 300mm Polargel MIXED-L column (Polymer Laboratories). The results are shown in the respective preparation examples.

The measurement temperature was 65 ℃, dimethylformamide was used as a solvent, and the flow rate was 1 mL/min. Samples were prepared at a concentration of 10mg/10mL and then fed in an amount of 100. mu.L. The Mw and Mn values were obtained with reference to a calibration curve formed using polystyrene standards. As polystyrene standards, 8 kinds having a molecular weight (g/mol) of 580/3,940/8,450/31,400/70,950/316,500/956,000/4,230,000 were used.

Preparation example 1 Synthesis of phthalonitrile oligomer (PN-1)

Phthalonitrile oligomer represented by the following chemical formula PN-1 was synthesized as follows.

41.1g of an oligomer represented by the formula KA-1 (weight average molecular weight 1,360g/mol) and 165.0g of DMF (dimethylformamide) were introduced into a 3-neck round-bottom flask, and the mixture was stirred at room temperature to dissolve. Thereto was added 51.9g of 4-nitrophthalonitrile, 70.0g of DMF was added, and then the mixture was stirred to dissolve. Subsequently, 49.8g of potassium carbonate and 30.0g of DMF were introduced together and the temperature was raised to 85 ℃ while stirring. After allowing the reaction to proceed for about 5 hours, the reaction solution was cooled to room temperature. The cooled reaction solution was poured into a 0.2N aqueous hydrochloric acid solution to neutralize and precipitate. After filtration, it was washed with water. The filtered solution was dried in a vacuum oven at 100 ℃ for one day. After removing water and residual solvent, phthalonitrile oligomer represented by the formula PN-1 (weight average molecular weight 2,000g/mol) was obtained in a yield of 95% by weight.

FIG. 1 shows the preparation of phthalonitrile oligomer PN-1¹H-NMR analysis results.

Preparation example 2 Synthesis of phthalonitrile oligomer (PN-2)

Phthalonitrile oligomer represented by the following chemical formula PN-2 was synthesized as follows.

48.0g of an oligomer represented by the formula NE-1 (weight-average molecular weight 1,600g/mol) and 165.0g of DMF (dimethylformamide) were introduced into a 3-neck round-bottom flask, and the mixture was stirred at room temperature to dissolve. To this were added 48.5g of 4-nitrophthalonitrile, 70.0g of DMF was added, and then the mixture was stirred to dissolve. Subsequently, 46.4g of potassium carbonate and 30.0g of DMF were introduced together and the temperature was raised to 85 ℃ while stirring. After allowing the reaction to proceed for about 5 hours, the reaction solution was cooled to room temperature. The cooled reaction solution was poured into a 0.2N aqueous hydrochloric acid solution to neutralize and precipitate. After filtration, it was washed with water. The filtered solution was dried in a vacuum oven at 100 ℃ for one day. After removing water and residual solvent, phthalonitrile oligomer represented by the formula PN-2 (weight average molecular weight 2,200g/mol) was obtained in a yield of 95% by weight.

FIG. 2 shows the preparation of phthalonitrile oligomer PN-2¹H-NMR analysis results.

Preparation example 3: synthesis of phthalonitrile oligomer (PN-3)

An oligomer represented by the formula PN-2 (PN-3) having a weight average molecular weight of 2,400g/mol was obtained in a yield of 96% by weight by the same method as in preparation example 2, except that the oligomer represented by the formula NE-1 having a weight average molecular weight of 1,700g/mol was used instead of the oligomer represented by the formula NE-1 (weight average molecular weight of 1,600 g/mol).

FIG. 3 shows the preparation of phthalonitrile oligomer PN-3¹H-NMR analysis results.

Preparation example 4 Synthesis of phthalonitrile oligomer (PN-4)

Phthalonitrile oligomer represented by the following chemical formula PN-4 was synthesized as follows.

48.6g of an oligomer represented by the formula NE-1 having a weight average molecular weight of 8,800g/mol and 155.0g of DMF (dimethylformamide) were introduced into a 3-neck round-bottom flask, and the mixture was stirred at room temperature to dissolve. To this were added 45.2g of 4-nitrophthalonitrile, 70.0g of DMF was added, and then the mixture was stirred to dissolve. Subsequently, 43.2g of potassium carbonate and 30.0g of DMF were introduced together and the temperature was raised to 85 ℃ while stirring. After allowing the reaction to proceed for about 5 hours, the reaction solution was cooled to room temperature. The cooled reaction solution was poured into a 0.2N aqueous hydrochloric acid solution to neutralize and precipitate. After filtration, it was washed with water. The filtered solution was dried in a vacuum oven at 100 ℃ for one day. After removing water and residual solvent, phthalonitrile oligomer represented by the formula PN-4 (weight average molecular weight 10,000g/mol) was obtained in a yield of 90% by weight.

FIG. 4 shows the preparation of phthalonitrile oligomer PN-4¹H-NMR analysis results.

Preparation example 5 Synthesis of phthalonitrile oligomer (PN-5)

Phthalonitrile oligomer represented by the following chemical formula PN-5 was synthesized as follows.

33.9g of an oligomer represented by the formula TD-1 (weight average molecular weight 2,700g/mol) and 164.0g of DMF (dimethylformamide) were introduced into a 3-neck round-bottom flask, and the mixture was stirred at room temperature to dissolve. Thereto were added 55.4g of 4-nitrophthalonitrile, 70.0g of DMF was added, and then the mixture was stirred to dissolve. Subsequently, 53.1g of potassium carbonate and 30.0g of DMF were introduced together and the temperature was raised to 85 ℃ while stirring. After allowing the reaction to proceed for about 5 hours, the reaction solution was cooled to room temperature. The cooled reaction solution was poured into a 0.2N aqueous hydrochloric acid solution to neutralize and precipitate. After filtration, it was washed with water. The filtered solution was dried in a vacuum oven at 100 ℃ for one day. After removing water and residual solvent, phthalonitrile oligomer represented by the formula PN-5 (weight average molecular weight 3,500g/mol) was obtained in a yield of 97% by weight.

FIG. 5 shows the preparation of phthalonitrile oligomer PN-5¹H-NMR analysis results.

Preparation example 6 Synthesis of phthalonitrile Compound (PN-6)

[PN-6]

23.3g of 4, 4' -dihydroxybiphenyl and 140g of DMF (dimethylformamide) were introduced into a 3-neck round-bottom flask, and the mixture was stirred at room temperature to dissolve. 43.3g of 4-nitrophthalonitrile was added thereto, 70.0g of DMF was added thereto, and then the mixture was stirred to dissolve. Subsequently, 36.3g of potassium carbonate and 30.0g of DMF were introduced together and the temperature was raised to 85 ℃ while stirring. After allowing the reaction to proceed for about 5 hours, the reaction solution was cooled to room temperature. The cooled reaction solution was poured into a 0.2N aqueous hydrochloric acid solution to neutralize and precipitate. After filtration, it was washed with water. The filtered solution was dried in a vacuum oven at 100 ℃ for one day. After removing water and residual solvent, the compound represented by the formula PN-6 (4, 4' -bis (3, 4-dicyanophenoxy) biphenyl) was obtained in a yield of 90% by weight.

FIG. 6 shows the preparation of PN-6 compounds¹H-NMR analysis results.

Preparation example 7 Synthesis of phthalonitrile Compound (PN-7)

[PN-7]

28.0g of bis (4-hydroxyphenyl) methane and 140g of DMF (dimethylformamide) were introduced into a 3-neck round-bottom flask, and the mixture was stirred at room temperature to dissolve. To this were added 48.5g of 4-nitrophthalonitrile, 50.0g of DMF was added, and then the mixture was stirred to dissolve. Subsequently, 46.4g of potassium carbonate and 30.0g of DMF were introduced together and the temperature was raised to 85 ℃ while stirring. After allowing the reaction to proceed for about 5 hours, the reaction solution was cooled to room temperature. The cooled reaction solution was poured into a 0.2N aqueous hydrochloric acid solution to neutralize and precipitate. After filtration, it was washed with water. The filtered solution was dried in a vacuum oven at 100 ℃ for one day. After removing water and residual solvent, the compound represented by the formula PN-7 (4, 4' - ((methylenebis (4, 1-phenylene)) bis (oxy)) diphthenzonitrile) was obtained in a yield of 95 wt%.

FIG. 7 shows the preparation of PN-7 compounds¹H-NMR analysis results.

Preparation example 8 Synthesis of curing agent (CA-1)

[ chemical formula a ]

[ chemical formula b ]

[ chemical formula c ]

24g of the compound of formula a and 45g of NMP (N-methyl-pyrrolidone) were introduced into a 3-neck round-bottom flask, and the mixture was stirred at room temperature to dissolve. It was cooled with a water bath, and 12.4g of the compound of formula b and 45g of NMP were added together in three portions. When the introduced compound was completely dissolved, 18g of toluene was added to the reaction solution to form an azeotrope. A Dean-Stark apparatus and reflux condenser were installed, and toluene was introduced and charged into the Dean-Stark apparatus. 4.2mL of pyridine was introduced as a dehydration condensation catalyst, the temperature was raised to 170 ℃ and the mixture was stirred for 3 hours.

While removing water generated by the formation of the imide ring with a Dean-Stark apparatus, the mixture was stirred for an additional 2 hours, and the residual toluene and pyridine were removed. The reaction product was cooled to room temperature and precipitated in methanol for recovery. The recovered precipitate was extracted with methanol to remove residual reactants and dried in a vacuum oven, thereby obtaining a CA-1 compound represented by chemical formula c in a yield of 81 wt%.

FIG. 8 shows the preparation of CA-1 compounds¹H-NMR analysis results.

Preparation example 9 preparation of curing agent (CA-2)

[CA-2]

A compound represented by the formula CA-2 (1, 3-bis (3-aminophenoxy) benzene; m-APB, manufactured by TCI Co., Ltd.) was prepared as a curing agent without further purification process.

Example 1

The phthalonitrile oligomer PN-1 was completely melted on a hot plate at 240 ℃ using an aluminum dish. A curing agent of the compound of formula CA-1 was added thereto so that it was present in an amount of about 0.15 mole per 1 mole of phthalonitrile oligomer PN-1. Further, the mixture was uniformly mixed on a hot plate at 240 ℃, and then cooled to prepare a 3D printing ink in a prepolymer state.

Example 2

A 3D printing ink in a prepolymer state was prepared by the same method as in example 1 except that a mixture of 50% by weight of phthalonitrile oligomer PN-1 and 50% by weight of phthalonitrile compound PN-7 was used in place of phthalonitrile oligomer PN-1. Wherein the curing agent of the compound of CA-1 is added so that it is present in an amount of about 0.15 moles per 1 mole of the mixture of PN-1 and PN-7.

Example 3

A 3D printing ink in a prepolymer state was prepared by the same method as in example 2 except that 10 parts by weight of silica and 10 parts by weight of graphite were also added based on 100 parts by weight of the mixture of the phthalonitrile oligomer PN-1 and the phthalonitrile compound PN-7.

Example 4

A 3D printing ink in a prepolymer state was prepared by the same method as in example 1 except that a mixture of 75 wt% of phthalonitrile oligomer PN-1 and 25 wt% of phthalonitrile compound PN-7 was used in place of phthalonitrile oligomer PN-1. Wherein the curing agent of the compound of CA-1 is added so that it is present in an amount of about 0.15 moles per 1 mole of the mixture of PN-1 and PN-7.

Example 5

A 3D printing ink in a prepolymer state was prepared by the same method as in example 4 except that 10 parts by weight of silica and 10 parts by weight of graphite were also added based on 100 parts by weight of the mixture of the phthalonitrile oligomer PN-1 and the phthalonitrile compound PN-7.

Comparative example 1

A 3D printing ink in a prepolymer state was prepared by the same method as in example 1 except that phthalonitrile compound PN-6 was used instead of phthalonitrile oligomer PN-1.

Comparative example 2

A 3D printing ink in a prepolymer state was prepared by the same method as in example 1 except that phthalonitrile compound PN-7 was used instead of phthalonitrile oligomer PN-1.

[ Table 1]

Experimental example 1: measurement of melt viscosity

The melt viscosities of the 3D printing inks prepared in examples and comparative examples were measured, and the results are shown in table 2 below.

Melt viscosity was measured by time sweep testing using a rotational rheometer at temperatures of 200 ℃ to 280 ℃ and frequencies of 1Hz to 10 Hz.

Experimental example 2: evaluation of printing characteristics

The 3D printing performance of the 3D printing inks prepared in examples and comparative examples was evaluated. The results are shown in table 2 below.

Using a 3D Printer (GEM-100, Coherent) at CO₂The 3D printing is performed under the conditions of laser, laser intensity of 1% to 5% and laser speed of 100 mm/sec to 1000 mm/sec.

Evaluation was performed according to the following criteria.

O: the 3D printing ink is cured by a laser, and a 3D structure may be formed.

And (delta): the 3D printing ink is cured by laser, but cannot form a 3D structure (not laminated).

X: the 3D printing ink is not melted by the laser, or is melted by the laser without solidifying.

[ Table 2]

	Melt viscosity (Pa.s)	3D printing characteristics
			Example 1	10000～100000	○
Example 2	1000～10000	△
			Example 3	10000～100000	○
Example 4	10000～100000	△
			Example 5	10000～100000	○
Comparative example 1	＜1	×
			Comparative example 2	＜1	×

Referring to table 2, it was determined that the 3D printing inks of examples 1 to 5 had significantly high melt viscosities as compared to comparative examples 1 and 2. In particular, it was determined that even though the 3D printing inks of examples 1 to 5 were melted by laser during 3D printing, they were rapidly solidified by laser scanning without shape collapse of the melted portion, thereby exhibiting excellent 3D printing performance.

Claims

1. A three-dimensional printing ink comprising (a) a phthalonitrile oligomer represented by any one of the following chemical formulae B to D and chemical formulae A-2 to A-3 and (B) a curing agent,

[ chemical formula B ]

[ chemical formula C ]

[ chemical formula D ]

In the chemical formulae B to D,

R¹to R⁴Each independently of the other is hydrogen, C_1-5Alkyl, or C_1-3Hydroxyalkyl, and L101 is a direct bond or unsubstituted or C_1-5Alkyl substituted C_1-5An alkylene group or a substituted alkylene group,

Z¹to Z⁵Each independently of the other is hydrogen or

And Z in each formula¹To Z⁵At least one of which is

The group of (a) or (b),

p1 is a number from 1 to 10,

n1 and m are the degree of polymerization of each repeating unit;

[ chemical formula A-2]

[ chemical formula A-3]

In the chemical formulae A-2 to A-3,

Z¹¹to Z⁶¹Each independently of the others is hydrogen or

And Z contained in each chemical formula¹¹To Z⁶¹At least one of which is

The group of (a) or (b),

L¹to L³Each independently is warp C_1-5Alkyl substituted C_1-5Alkylene, and

n2 is the degree of polymerization of each repeating unit.

2. The three-dimensional printing ink according to claim 1, wherein the chemical formula B is represented by the following chemical formula B-1,

[ chemical formula B-1]

In the chemical formula B-1, the metal oxide,

Z¹²to Z⁵²Each independently of the others is hydrogen or

And Z contained in the chemical formula B-1¹²To Z⁵²At least one of which is

Group (d) of，R¹And L101 is the same as that defined in claim 1, and

n3 is the degree of polymerization of the repeating unit.

3. The three-dimensional printing ink according to claim 1, wherein the chemical formula C is represented by the following chemical formula C-1,

[ chemical formula C-1]

In the chemical formula C-1, the metal oxide,

Z¹³to Z⁵³Each independently of the others is hydrogen or

And Z contained in the chemical formula C-1¹³To Z⁵³At least one of which is

A group of (A), and

n3 and m3 are the respective degrees of polymerization of the respective repeating units.

4. The three-dimensional printing ink according to claim 1, wherein the chemical formula D is represented by the following chemical formula D-1,

[ chemical formula D-1]

In the chemical formula D-1, the metal oxide,

Z¹⁴to Z³⁴Each independently of the others is hydrogen or

And Z contained in the chemical formula D-1¹⁴To Z³⁴At least one of which is

The group of (a) or (b),

p2 is 1 to 10, and

n4 is the degree of polymerization of the repeating unit.

5. The three-dimensional printing ink according to claim 1, wherein the phthalonitrile oligomer has a weight average molecular weight of from 1,000 to 30,000 g/mol.

6. The three-dimensional printing ink according to claim 1, further comprising (a') a phthalonitrile compound represented by the following chemical formula P1,

[ chemical formula P1]

In the chemical formula P1, R^P11To R^P16Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, a group of the formula P2 below or a group of the formula P3 below, and R^P11To R^P16Two or more of which are a group of the following formula P2 or a group of the following formula P3,

[ chemical formula P2]

In the chemical formula P2, the chemical formula P,

R^P21To R^P25Each independently of the other is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, or cyano, and R^P21To R^P25Two or more of which are cyano groups,

[ chemical formula P3]

In the chemical formula P3, the chemical formula P,

R^P31To R^P35Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, or a group of the formula P2, and R^P31To R^P35One or more of which are groups of the formula P2.

7. The three-dimensional printing ink according to claim 1, wherein the curing agent has one or more functional groups selected from the group consisting of amine groups, hydroxyl groups, and imide groups.

8. The three-dimensional printing ink according to claim 7, wherein the curing agent is a compound represented by the following chemical formula 2,

[ chemical formula 2]

In the chemical formula 2, R²¹To R²⁶Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, amine, or a group of the following chemical formula 3, and R²¹To R²⁶Two or more of which are amine groups or groups of the following chemical formula 3,

[ chemical formula 3]

In the chemical formula 3, the reaction mixture is,

L³⁰is a direct bond, C_1-5Alkylene, -O-or-S-, and

9. The three-dimensional printing ink according to claim 7, wherein the curing agent is a compound represented by the following chemical formula 4,

[ chemical formula 4]

In the chemical formula 4, the first and second organic solvents,

X⁴¹and X⁴²Each independently is a divalent group derived from a compound represented by any one of the following chemical formulae 8 and 9, and

n5 is equal to or greater than 1;

[ chemical formula 5]

In the chemical formula 5, R⁵⁰To R⁵⁵Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy, or C_6--30An aryl group;

[ chemical formula 6]

In the chemical formula 6, R⁶⁰To R⁶⁷Each is independent of othersThe ground is hydrogen or C_1-5Alkyl radical, C_1-5Alkoxy, or C_6-30An aryl group;

[ chemical formula 7]

In the chemical formula 7, the first and second organic solvents,

x is a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -S (═ O)₂-、-C(＝O)-O-L¹⁷-O-C(＝O)-、-L²⁷-C(＝O)-O-L³⁷-、-L⁴-O-C(＝O)-L⁵-, or-L⁶-Ar¹-L⁷-Ar²-L⁸-, wherein L¹To L⁸Each independently is a direct bond, -O-, or C_1-5Alkylene, and Ar¹And Ar²Each independently is C_6-30An arylene group;

[ chemical formula 8]

In the chemical formula 8, R⁸⁰To R⁸⁵Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, hydroxy, or carboxy;

[ chemical formula 9]

In the chemical formula 9, the first and second organic solvents,

R⁹⁰to R⁹⁹Each independently is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy radical, C_6-30Aryl, hydroxy, or a salt thereof,Or a carboxyl group,

x' is a direct bond, C_1-5Alkylene, -O-, -S-, -C (═ O) -, -NR^a1-、-S(＝O)-、-S(＝O)₂-、-L⁹-Ar³-L¹⁰-, or-L¹¹-Ar⁴-L¹²-Ar⁵-L¹³-, wherein R^a1Is hydrogen, C_1-5Alkyl radical, C_1-5Alkoxy or C_6-30Aryl radical, L⁹To L¹³Each independently is a direct bond, -O-, or C_1-5Alkylene, and Ar³To Ar⁵Each independently is C_6-30An arylene group.

10. The three-dimensional printing ink according to claim 1, wherein the curing agent is contained in a molar ratio of 0.01 to 1.5 moles per one mole of the phthalonitrile oligomer.

11. The three-dimensional printing ink according to claim 1, wherein the three-dimensional printing ink exhibits a melt viscosity of 1000 Pa-s to 100000 Pa-s using a rotational rheometer at a temperature of 200 ℃ to 280 ℃ and a frequency of 1Hz to 10Hz through a time sweep test.